Polymers of dialkyl methallyliminodialkanoates



POLYMERS OF DIALKYL METHALLYLIMINO- DIALKANOATES William O. Forshey,Jr., New Castle, DeL, assignor to E. I. du Pont de Nemours and Company,Wilmington, Del., a corporation of Delaware No Drawing. Application May15, 1952, Serial No. 288,015

12 Claims. (Cl. 260-2.1)

This invention relates to addition polymers and more particularly toacrylonitrile copolymers.

Tertiary amines such as vinylpyridine have been employed incopolymerization with acrylonitrile to provide improved dyeability suchas described in U. S. 2,491,471. More recently, quaternary ammoniumcompounds have been found to further improve the dyeability of many ofthe corresponding copolymers. Although these discoveries advance the artof obtaining dyeable textiles of desirable inertness to water,dry-cleaning agents, etc., the improvement at times is at the expense ofother properties. Thus, the quaternary compounds when copolymerized withacrylonitrile can give rise to undesirable colors, particularly onheating as require in conventional methods for the fabrication of thepolymer. Copolyrners having simple quaternary ammonium units tend toexhibit a lack of thermal stability, particularly after soaping or othermild alkaline treatments. This defect is of importance where thecopolymer is intended for textile or similar applications since thealkaline environment of washing followed by subsequent thermal treatmentis comparable to that of conventional washing and ironing procedure. Itis of course highly desirable for many applications that textileproducts not deteriorate under such treatment.

This invention has as an object the preparation of polymers. A furtherobject is the preparation of an acrylonitrile copolymer possessingresistance to Water and drycleaning agents, superior stability to alkaliand heat treatments, and the ability to be modified by dyes, forexample, with acid dyes. Another object is the preparation of anacrylonitrile copolymer having units of a comenomer. Other objects willappear hereinafter.

These objects are accomplished by the present invention of new additionpolymers characterized by repeating units, mers, of a tertiary aminewhich has attached to one of the three valences of the nitrogen anallylic hydrocarbon radical, i. e., a monovalent aliphatic hydrocarbonradical of three to four carbons and of three chain carbons having butone unsaturation and that in a terminal ethylenic group, i. e., avinylidene group bonded to the nitrogen through one methylene group, atleast one of the remaining valences of said nitrogen being attachedthrough a carbon containing chain of one to four carbons to at least onecarbalkoxy group (wherein the alkoxy is of a lower (one to four carbon)alkyl), any remaining valence of the nitrogen being satisfied by a loweralkyl radical. Particularly useful monomers are those of the generalformula from monomers of the above general formula. The more 2,739,949Patented Mar. 27, 19565 useful polymeric materials are those wherein Ris a divalent hydrocarbon radical of at least two chain carbons betweenits free valences and m equals 2, i. e., polymeric materials having aplurality of units of the formula CHz=CCH2N(R--COOR)2 Such areespecially useful in view of their availability,

ease of polymerization to polymers which are readily dyed.

and are stable to the deleterious effects of heat after mild alkalinesoap treatment, and particularly the acrylonittile copolymers whichcontain from 0.5 to 10% of monomeric units of the above class. Suchacrylonitrile copolymers generally have a molecular weight of at least5000 and as high as 100,000 or higher.

The polymers, and particularly the copolymers, of this invention areobtained by the polymerization of the monomers, preferably in thepresence of other polymerizable ethylenically unsaturated compounds,employing catalytic amounts of a free radical-generating polymerizationcatalyst to initiate the polymerization.

The following examples in which parts are by weight are illustrative ofthe invention.

EXAMPLE I Acrylonitrile/dimethyl allyliminodipropionate (/5) copolymerTo a solution of 0.342 parts of potassium dihydrogen phosphate in 190parts of distilled water of pH of 7.0, was added 13 parts ofacrylonitrile, 0.685 part of dimethyl allyliminodipropionate, 0.1888part of thiourea and 5.68 parts of 3% hydrogen peroxide. The reactionmixture was flushed with nitrogen and the reaction bottle sealed. Afterstanding with occasional shaking at room temperature for three hours,the reaction mixture was filtered and the white copolymer was washedwith distilled water, then with 200 parts of methanol containing 2 partsof concentrated hydrochloric acid and finally with parts of methanol. Atotal of 7.8 parts of copolymer was obtained having an inherentviscosity (0.2% in dimethylformamide) of 1.23. A film of this copolymerprepared by casting from a 15% solution in dimethylformamide exhibitedvery good dye receptivity to acid-type dyes in a dye bath having a pH of3.0. This copolymer exhibited very good thermal stability both beforeand after a boiloil in /2 soap solution for /2 hour. Heating a boiledofffilm sample for 20 minutes at C. resulted in essentially no thermaldecomposition of the copolymer.

EXAMPLE II Acrylonitrile/dimethyl allyliminodiacetate (95/5) 00- polymer1.18 (0.2% in dimethylformamide). The properties of the copolymer weresubstantially the same as of the copolymer of Example I except the dyereceptivity was not as high.

EXAMPLE III Acrylonitrile/dimethyl methallyliminodiacetate (92.65 7 .35copolymer This copolymer was prepared using the system described inExample I and using the same quantities of reagents with the exceptionthat 1.03 parts of dimethyl methallyl- 3 irninodiaeetate was used as thecomonomer. Erom this polymerization system a total of 2.5 parts ofacrylonitrile/dimethyl methallyliminodiacetate copolymer was obtained.The properties of the copolymer were substantially the same as those ofExample '11.

EXAMPLE 1v Aczyl6niffil/dim'eth'yl n 1etliallyliinihdiiiprbpiofilite(95/5) copolymer This copolymer was prepared using the proceduredescribed in Example I. A total of 6.0 parts of this copolymerwasobtained from a reaction system cont'ain'iiig "0.342 part erpotassium dihyd I l i 0 01635 part of 'diniethyl inethallylirn'inodir'irparts of 'acrylonitrile, 0.1258 part o f jthiour a rid"3 .78 parts of-3%hydrogen peroxide in 190""pa'rfs of distilled water.The*copolymerobtained had 'aninherent'viseosity of 1559 "(0.2% in dimethyl formarnidw and exhibited eX c'ell'ent'dye receptivity to acid typedyes over 'thei pH range of 3.0 o 5.6. This copolyr'ne'r alsoshj'owede'ss'ehtially'no thermal-accom anist] when boiled for /2 hour tea/1% soapsolution followed byaessngrer 20 names at1'65C.

This invention is generic polymersfo'f tertiary a'i r'iih'es which haveattached to 'or'ie yalence of the nitrogh an allyl or methallyl radical,-i. "e., "a 'mdriova'le'nt aliphatic h'ydrocarbon tadic'ai 6f three toremembers aiid'three chain carbons having but one unsatiiratioh and thatin a terminal ethylenic group, or 'yinylidene, CH2=C group bondedthrough one methylene group to the nitrogen and also attached to atleasfone of 'the vale nc es of the nitrogen through a carbon containingchain of one to four carbons at least'on'e carbalkoxy group wherein thealkoxy is of 'a lower (one to four carbon) alkyl radical, any remainingvalence of the nitrogen being satisfied by a lower (one to four carbon)alkyl radical. The polymeric materials of the present invention arecharacterized by those which have a plurality of repeating units, ormers, of a monomer of the general formula R2'In otr o orL-N wherein itis a cardinal number of up to one, "m is *a'n integer or up to two, R isa lower alkyl radic'al aiid R is a divalent hydrocarbon radical of up"to'foiir carbons.

The more useful adnbmers which are employed "to give polymers andparticularly copolyrri'ers of this "invenaerate those wherein R is adivalent saturated aliphatic tr -sidearm; radical of'at l'e'ast'twochain carbons between its fiee valenc'es and m equals 2.Theser'nonorn'ers are iminobis'dialkanoic acid esters wherein the thirdvalence of the nitrogen is attached to a three to four carbon, threechain carbon, monovalent aliphatic hydrocarbon radical haying'biitdneunsannatien and that of "a'viiiyndene group attached through onemethylene group to th nitrogen. These have the formula 1 E Particularlyvaluable co'polymers with 'ethylenically unsaturated monomers, areobtained by the copolymerization of the lower (one to four carbon) alkyldie'sters 'of-allyliminoa and methallylhninodipropionic and dibutyricacids. Thus, the methyl, ethyl, butyl esters can =be"em'- ployed.

The monomeric tertiary allyland methallylamines having carboxyl estersubstituents which are the monomers aaaeetabnotnefrs of the polymers ofthis iiive'ntion can be prepared by the addition of an ester of analpha, betai ethylenicallyunsaturated acid to an allyl or-'rr'x'ethallylamine whichhas at least one hydrogen and preferablytwohydrogens on the nitrogen. See the copending'application, Serial No.288,011, filed May 15, 1952, by

Theodore L. Cairns, now abandoned. This addition is illustrated by theaddition of methyl acrylate, methyl methacrylate, etc., to allylormethallylamines, e. g., allylamine, methallylamine,N-methylmethallylamine, N- butylrnethallylamine, etc. A further methodconsists in the reaction of allylor methallylarhine with a sewer alkylester of a monohalogenated lower alkanoic acid wherein the halogen ischlorine, bromine or'io dine, e. g, ethyliiio iidchloroacetafe, butylmonohrornoacetategme thyl g'a'r'nrria -bromo-n-butyrate,propyliodoacetate, etc. The reaction is carried out in the presence ofan acid acceptor. A polymerization inhibitor is generally present duringthese reactions. Additional specific'tertiary amines which can bepolymerized and copolymerized to give the polymers, includingcopolymers, of this invention are methyl methylrnethallylaminoacetate,dibutyl methallyliminodh propiohate and dimethyl'm'e'thallylirninodi(heta ethylpropionate).

p The polymerization of the carhalltoity-containing allylic tertiaryamines can becar'ried out with cdnv'er it idnalpolymeriz'atiohcatalysts. Ionic catalysts can be employed, particularly in thehomopolymeriiation of these com pounds. Copoly'merizati'on is howevergenerally conducted with a fr'ee radical catalystye. g., an "'azo'orperoxy compound or similar systems which initiate polymerization byformation of tree radicals.

While the homop'olymers of "the prcsent'in'vention are of some utilityin ion exchange resins, the principally useful polymers are thecopolymers with addition polynieriz'a'hle -'ethyl'enic'all y unsaturatedmonomers, particularly those having 'but one entyienic summaries. inthese copolymers as little as 0.1% of the allylic tertiaryaminecarboirylic ester can produce a definite efiect'o'n dyeability.While this is of use in copol'yn'r' ers with, for example, vinylchloride, vinylacetate, styrene, vinylidene chloride, r'iiethylm'ethacrylate, etc., a particularly important class of polymers is thatobtained by the copolynierizationof acrylonitrile 'with from 0.1 to 10%,based onthe 'aerylonitrile, of the tertiary amine having am: valencebo'rided -"to a three to four carbon, three chain carbon,=n'ion'o'valent aliphatic hydrocarbon radical whos c 1 ohlyiinsaturation is that of a vinylidene 'group'attached thr'du g'h'o n'emethylene-group to the nitrogen, at least one remaining valence of whichis attached, through 'a-carbon containin'g'chainof-oneto four carbons,preferably hydrocarbon of 'at least two chain carbons between the freevalencfes, to at least one carboxyl group 'e'sterified with a loweralkan'ol, "any remaining valence being satisfied by "a ldw'e'r 'alkylgrou Particularly useful are these cop'olyhiers wherein 'the allylicairline is a die'ster of allyliminoor rnet'hallyliminodipropionic or dibutyric "acid ahdfthe esterifyin'g alkyl is methyl o'rethyl.T'hese'copo'lyiiiefs fdr utility in textiles should have a 'rriolecularweigriref "atleast5000 and the molecular weight can be M gha's -10 0,000or more. Copolyir1e rs of "this'type 1i p-eribrnye receptivity to acid-type dyes and stability ttfheat after treating with soap. Theseeopoly- 6am h'edyed with acid-ityp'edyes under varying eondi'tior'is ofacid, 'for example, the *dyeability relatively eenasm'witmn me range ofpH Zto pH 5 with acid dyes. pret'err ed from the standpoint ofp'rciperties polymer are those which containtrom 1 dftheallylamihesuChasQfor Xanipladiniet'hylinethallyliminodipropionate.

The foregoing detailed description has been given for clearness ofunderstanding only and no unnecessary limitations are to be understoodtherefrom. The invention is not limited to the exact details shown anddescribed for obvious modifications will occur to those skilled in theart.

1. Apolyt'ner of a die'str, with "aloweralkanol bf-"anN-methallyliminodiallianoic acid wherein the allianoic' acid radicalsare of upto live carbons.

2 A polymer of a lower alkyl diester of N-methallyliminodipropionicacid.

3. A polymer of a diester, with a lower alkanol, of anN-allyliminodialkanoic acid wherein the alkanoic acid radicals are of upto five carbons.

4. A polymer of a diester, with a lower alkanol, of an iminodialkanoicacid wherein the third valence of the imino nitrogen, that not bonded tothe alkanoic radicals, is bonded to a three to four carbon, three chaincarbon, monovalent aliphatic hydrocarbon radical whose only unsaturationis that of a vinylidene group attached through one methylene group tothe nitrogen.

5. An acrylonitrile copolymer, of improved dyeing properties, containing0.1 to based on the weight of the acrylonitrile, of units of a diester,with a lower alkanol, of an iminodialkanoic acid wherein the thirdvalence of the imino nitrogen, that not bonded to the alkanoic radicals,is bonded to a three to four carbon, three chain carbon, monovalentaliphatic hydrocarbon radical whose only unsaturation is that of avinylidene group attached through one methylene group to the nitrogen.

6. A polymer of a tertiary amine which has but one carbon to carbonunsaturation and wherein one valence of the amino nitrogen is bonded toa three to four carbon, three chain carbon, monovalent aliphatichydrocarbon radical having one unsaturation and that of a vinylidenegroup bonded, through one methylene group, to the nitrogen which has atleast one other valence bonded, through a chain containing one to fourcarbons to at least one carboxyl group esterified with a lower alkanol,any remaining valence of the nitrogen being satisfied by a lower alkylgroup.

7. A copolymer of acrylonitrile containing 0.1 to 10%, based on theweight of the acrylonitrile, of a tertiary amine which has but onecarbon to carbon unsaturation and wherein one valence of the aminonitrogen is bonded to a three to four carbon, three chain carbon,monovalent aliphatic hydrocarbon radical having one unsaturation andthat of a vinylidene group bonded, through one methylene group, to thenitrogen which has at least one other valence bonded, through a chaincontaining one to four carbons to at least one carboxyl group esterifiedwith a lower alkanol, any remaining valence of the nitrogen beingsatisfied by a lower alkyl group.

8. A polymer of a tertiary amine wherein one valence of the aminonitrogen is bonded to a three to four carbon,

three chain carbon, monovalent aliphatic hydrocarbon radical having oneunsaturation and that of a vinylidene group bonded, through onemethylene group, to the nitrogen which has at least one valence bondedthrough a bivalent saturated aliphatic hydrocarbon radical of one tofour carbons to a carboxyl group esterified with a lower alkanol, anyremaining valence of the nitrogen being satisfied by a lower alkylgroup.

9. A copolymer of acrylonitrile containing 0.1 to 10%, based on theweight of the acrylonitrile, of a tertiary amine wherein one valence ofthe amino nitrogen is bonded to a three to four carbon, three chaincarbon, monovalent aliphatic hydrocarbon radical having one unsaturationand'that of a vinylidene group bonded, through one methylene group, tothe nitrogen which has at least one valence bonded through a bivalentsaturated aliphatic hydrocarbon radical of one to four carbons to acarboxyl group esterified with a lower alkanol, any remaining valence ofthe nitrogen being satisfied by a lower alkyl group.

10. A polymer of a diester, which diester has the formula 0H2:OHzN(AlkyleneC o O-Lower AlkyDg wherein n is a cardinal number notgreater than one.

11. An acrylonitrile copolymer, of improved dyeing properties,containing 0.1 to 10%, based on the weight of the acrylonitrile, ofunits of a diester, which diester has the formula given in claim 10.

12. An acrylonitrile copolymer, of improved dyeing properties,containing 0.1 to 10%, based on the weight of the acrylonitrile, ofunits of a diester, with a lower alkanol, of N-methallyliminodipropionicacid.

References Cited in the file of this patent UNITED STATES PATENTS2,258,718 Rothrock Oct. 14, 1941 2,327,985 Alderman et a1 Aug. 31, 19432,378,169 Agre et al June 12, 1945 2,601,251 Bruson June 24, 19522,628,224 Cairns et a1 Feb. 10, 1953 OTHER REFERENCES Chemical Abstracts43, 2226 (1949).

6. A POLYMER OF A TERTIARY AMINE WHICH HAS BUT ONE CARBON TO CARBON UNSATURATION AND WHEREIN ONE VALENCE OF THE AMINO NITROGEN IS BONDED TO A THREE TO FOUR CARBON, THREE CHAIN CARBON, MONOVALENT ALIPHATIC HYDROCARBON RADICAL HAVING ONE UNSATURATION AND THAT OF A VINYLIDENE GROUP BONDED, THROUGH ONE METHYLENE GROUPS, TO THE NITROGEN WHICH HAS AT LEAST ONE OTHER VALENCE BONDED, THROUGH A CHAIN CONTAINING ONE TO FOUR CARBONS TO AT LEAST ONE CARBOXYL GROUP ESTERIFIED WITH A LOWER ALKANOL, ANY REMAINING VALENCE OF THE NITROGEN BEING SATISFIED BY A LOWER ALKYL GROUP. 